CONCERTED MECHANISM OF THE AMINOLYSIS OF O-ETHYL S-(2,4-DINITROPHENYL) THIOCARBONATE

被引：92

作者：

CASTRO, EA

IBANEZ, F

SALAS, M

SANTOS, JG

机构：

[1] Facultad de Quimica, Pontificia Universidad Católica de Chile, Santiago

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1991年 / 56卷 / 16期

关键词：

D O I：

10.1021/jo00016a002

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The linear Bronsted-type plot with slope beta = 0.56 found in the aminolysis of O-ethyl S-(2,4-dinitrophenyl) thiocarbonate indicates a concerted mechanism, which is explained through instability of the putative zwitterionic tetrahedral intermediate, caused by the EtO group. Had the mechanism been stepwise the position of the Bronsted break should have been at pK(a) 9.3 (the experimental pK(a) range is 6.4-11.5).

引用

页码：4819 / 4821

页数：3

共 32 条

[1] THE MECHANISM OF THERMAL ELIMINATIONS .19. RATE DATA FOR PYROLYSIS OF S-ARYL O-ETHYL THIOCARBONATES - THE RELATIVE ABILITIES OF OXYGEN AND SULFUR TO TRANSMIT ELECTRONIC EFFECTS
ALAWADI, N
TAYLOR, R
[J]. JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1986, (10): : 1581 - 1583
[2] CONCERTED ACETYL GROUP TRANSFER BETWEEN SUBSTITUTED PHENOLATE ION NUCLEOPHILES - VARIATION OF TRANSITION-STATE STRUCTURE AS A FUNCTION OF SUBSTITUENT
BASAIF, S
LUTHRA, AK
WILLIAMS, A
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (07) : 2647 - 2652
[3] Bell R. P., 1959, PROTON CHEM, P159
[4] KINETICS OF REACTION OF P-NITROPHENYL METHYL CARBONATE WITH NUCLEOPHILES IN AQUEOUS-SOLUTION, AND RELATIVE EASE OF ACETYL AND METHOXYCARBONYL TRANSFER-REACTIONS
BOND, PM
MOODIE, RB
[J]. JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1976, (06): : 679 - 682
[5] KINETICS OF REACTION OF SUBSTITUTED PYRIDINES AND OXYGEN ANIONS WITH METHYL CHLOROFORMATE IN AQUEOUS-SOLUTION
BOND, PM
CASTRO, EA
MOODIE, RB
[J]. JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1976, (01): : 68 - 72
[6] A SINGLE TRANSITION-STATE IN THE REACTION OF ARYL DIPHENYLPHOSPHINATE ESTERS WITH PHENOLATE IONS IN AQUEOUS-SOLUTION
BOURNE, N
CHRYSTIUK, E
DAVIS, AM
WILLIAMS, A
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (06) : 1890 - 1895
[7] EVIDENCE FOR A SINGLE TRANSITION-STATE IN THE TRANSFER OF THE PHOSPHORYL GROUP (-PO3-O-2-) TO NITROGEN NUCLEOPHILES FROM PYRIDINO-N-PHOSPHONATES
BOURNE, N
WILLIAMS, A
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1984, 106 (24) : 7591 - 7596
[8] CABRERA M, IN PRESS J ORG CHEM
[9] CURVED BRONSTED PLOT IN PYRIDINOLYSIS OF 2,4-DINITROPHENYL METHYL CARBONATE - COMPARISON OF LEAVING GROUP ABILITIES BETWEEN PYRIDINES AND PHENOLATES
CASTRO, EA
GIL, FJ
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1977, 99 (23) : 7611 - 7612
[10] STRUCTURE-REACTIVITY CORRELATIONS IN THE AMINOLYSIS OF PHENYL AND PARA-NITROPHENYL THIOLACETATES
CASTRO, EA
URETA, C
[J]. JOURNAL OF ORGANIC CHEMISTRY, 1989, 54 (09) : 2153 - 2159

← 1 2 3 4 →